If you are trying to send an email from an old isp mail account, using a different isp email connection; you have to change the mail.smtp settings, for the settings you will need to refer to your isp.
If you are trying to send an email using a hotmail account, this can no longer be done as hotmail no longer allow the use of outlook express with their accounts

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Related Questions:

·You import mail from Outlook into Outlook Express, but you removed Outlook from your computer before you tried to import the mail into Outlook Express.
·You configure Outlook Express to be the default Simple Messaging application programming interface (MAPI) client.
·You import or export mail from Outlook Express, and you do not have Outlook installed on your computer.
To resolve this issue, try one of the following methods, as appropriate for your situation.

Method 1: If you want to use a special program you can use Outlook Express Fix Toolbox

Method 2: Change your MAPI Settings

Configure Outlook Express to not be the default Simple MAPI client before you import the mail items. To do this, follow these steps:
1.Restart your computer, and then start Outlook Express.
2.On theToolsmenu, clickOptions.
3.On theConnectiontab, clickChangeto open theInternet Propertiesdialog box.
4.On theProgramstab, click an e-mail application other than Outlook Express in theE-maillist. ClickApply, and then clickOK.
5.ClickOKagain to close theOptionsdialog box.
6.Exit Outlook Express, and then restart Outlook Express.